University of Oulu

Mmushi M. Moeng, Frederick P. Malan, Simon Lotz, Daniela I. Bezuidenhout, Fischer carbene complexes of cobalt(I): Synthesis and structure, Journal of Molecular Structure, Volume 1252, 2022, 132093, ISSN 0022-2860, https://doi.org/10.1016/j.molstruc.2021.132093

Fischer carbene complexes of cobalt(I) : synthesis and structure

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Author: Moeng, Mmushi M.1; Malan, Frederick P.1; Lotz, Simon1;
Organizations: 1Department of Chemistry, University of Pretoria, Private Bag X20, Hatfield 0028, Pretoria, South Africa
2Laboratory of Inorganic Chemistry, Environmental and Chemical Engineering, University of Oulu, P.O. Box 3000, 90014 Oulu, Finland
Format: article
Version: published version
Access: open
Online Access: PDF Full Text (PDF, 1.3 MB)
Persistent link: http://urn.fi/urn:nbn:fi-fe202201051214
Language: English
Published: Elsevier, 2022
Publish Date: 2022-01-05
Description:

Abstract

Three different aryl substrates thiophene (ThH), ferrocene (FcH) and p-bromodimethylaniline (p-DMABr) were lithiated and reacted with [Co(CO)₄SnPh₃], according to the Fischer carbene protocol. The products [CoSnPh₃(CO)₃{C(OEt)R}] (R =Th, 1, p-DMA, 2 and R = Fc, 3) were analysed to unravel the role of the aryl carbene substituent in stabilizing intermediates and final products. The ethoxy carbene complexes were aminolysed by in situ generated HNMe₂ to afford [CoSnPh₃(CO)₃{C(NMe₂)R}] (R =Th, 4, p-DMA, 5) and with N,N-dimethylethylenediamine [CoSnPh₃(CO)₃{C(NHCH₂CH₂NMe₂)R}] (R = p-DMA, 6) in high yields. The trigonal Co(CO)₃ in the equatorial plane is very stable and efforts to displace a carbonyl in 6 was unsuccessful, both by heating and irradiation. The role of the aryl carbene substituents in stabilizing the electrophilic carbene carbon was investigated and studied by NMR spectroscopy in solution and single crystal X-ray structure determinations.

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Series: Journal of molecular structure
ISSN: 0022-2860
ISSN-E: 1872-8014
ISSN-L: 0022-2860
Volume: 1252
Article number: 132093
DOI: 10.1016/j.molstruc.2021.132093
OADOI: https://oadoi.org/10.1016/j.molstruc.2021.132093
Type of Publication: A1 Journal article – refereed
Field of Science: 116 Chemical sciences
Subjects:
Funding: The authors gratefully acknowledge the National Research Foundation, South Africa [NRF 105740; NRF 105529 NRF 87788 and NRF 9772] and Sasol Technology R&D Pty. Ltd. (South Africa) for financial support.
Copyright information: © 2021 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/) .
  https://creativecommons.org/licenses/by/4.0/